Process for forming nitrogen compounds.



L. L. SUMMERS., PROCESS FOR FORMINO NITROGEN COMPOUNDS.; APPLICATION FILED APR. 22. I9I4l l Patented Oct. 9, 1917.

rcentral cone and supplied with 'which may be turned by hand wheel 26 or power driven mechanism as preferred to slowly rotate the furnace. The upper end ,27 of the cone ,is preferably made of fire brick or similar lrefractory material which covers a circular electrode 3e of carbon or other suitable conducting material which is supported upon a plate or disk 29 of insulating material, An insulating sleeve 30 extends through the electrode at its center and the parts are maintained in position by a central bolt 3i. A bus-bar or conductor 32 extends axially through the cone` is branched atits upper end and connected to said electrode. rl`he cone has an axial chaniber, as shown in the dravvinc', through whichpsaid conductor extends, and a plug 33 of mica or Aother suitable insulating material spaces the conductor from the adjacent Walls of said chamber at theuloiver end thereof. An an nular Water chamber' 2a is 'formed Within the water throughv the connections 2b. 'lhc rotary member of the furnace is provided with an annular plate electrode 34 of carbon or other similar material located in the same plane as the electrode 2S and conductors or bus-bars 35 connect the same with the generator which supplies the furnace with elec- -tric energy. Twyers 3G supplied by pipes 36 openinto the annular passage about the central cone below the electrodes and serve to furnish air or other gas to the material being,- treated at this level. By reason of the shape of the interior cone and the interior Wall of the revoluble member of the furnace the passage for the material. being treated between said elements gradually converges to a level below the electrodes and twyers and then diverge. slightly and openings are formed through the stationary member of the furnace and through the sup por ting plate 38 therefor through which the material being treated may escape. Plate 38 is supported upon standards 39 and tracks l0 are preferably provided so thata car Lil may be run beneath the furnace and the material being treated be allowed to fall into the same, an annular funnel Ll2 being provided to direct the latter.

IThe material beingl treated is maintained in the furnaceto a level above that of the electrodes, and having a considerable resistance, as it passes Said electrodes, is highly heated by the current passing therethrough. The heating action is assisted when air or other oxidizing; agent is introduced through the tivyers by the combustion of the carbonaeeous material forming av part of the charge, es it drops below the tufyers, however, it is rapidly cooled and ground by the Water-cooled grinding plates or .facings 9, l@ and ultimately reaches the discharge openings 37 in a finely .divide-d condition. n

The operation of the process and appai n. 'arose r ioxi loing i l d ratus is follows; mil-:ed with an excess of powdered coal or coke is placed in the furnace to a depth covering' the electrodes, the hoppers 13 are also lled, the current is turned on. andas both the coke and manganese dioxid are conductors, the material is quickly heated to a bright red heat. 'lhe twyers 16 are then opened and preheated air is allowed to enter the furnace causing' an intense combustion below the electrodes. The teniperature .is then adjusted by controlling1 the current so that the material will have a temperature oi' from i090@ to i500@ C. depending on the materials used and conditions of operation. As the manganese dionid is heated in the presence of carbon, the tendency is to reduce the foriner to a metallic condition but owing to the excess of carbon present. the resulting` reaction is the forn'iation of a carbid of manganese which, like all metal carbide having' a lower meltingpoint than the metal itself readily fuses under the temperature used. Manganese forms a number of distinct compounds with carbon, all being known as carbide, and represented by the formulas ll/lngC7 Mn@ li/lntlg, etc. Upon further heating these carbide the manganese is vaporized and the carbon is precipitated as Graphite. y icl/hen atmospheric nitrogen is brought into' conn tact with the highly heated mixture of carbon and manganese, there formed varions nitrids of manganese, the vapor of nascent manganese released from the carbids'also reforming higher carbide. rThe exact'. reactions at these temperatures are very complex and uncertain, and the above reactions are further complicated by the fact that the carbide and the carbon thereof unite With the nitrogen to form various The final n monia.. ln practice the compounds distilled are obtained in the forni of both cyancgen compounds and ammonia, as Well as corr.- pounds resulting from nitric oxid, NU.

llhe advantages of manganese' the metal employed in the process above de scribed are numerous. The ease with which manganese carbide are formed makes possible to use lower temperatures than is p sible with the alkali or alkaline earth metals, and 'further manganese has a dis tinct advantage in readily forming nitride, carbids, and cya-mogen compounds. The metal also exerts pronounced catalytic effeet on nitrogen. ln general these reactions start at 10G()o to 1100@ C. and at 13000 to M00O C. volatile products carrying combined nitrogen are readily distilled. The exact nature of these products is difficult to determine but in general they are compounds of manganese, carbon and nitrogen while the gas from the fuel is largely carbon monoxid and nitrogen, the oxygen of the air and the oxygen of the oxids both uniting with the excess of carbon which is present. llhen coal is used or producer gas is blown in through the twyers 3S', the hydrogen present acts to form derivations of hydrocyanic acid. y

By the use of preheated air in the twyers 36', it is possible to produce a temperature capable of combining vthe other elements" named with the atmospheric nitrogen withw out the electric resistance furnace, but the products of combustion are then excessive and the presence of the large amount of C@ and C02 in the furnace gases, causes an eX- cessive oxidizing reaction to ltake place, tending to deposit the volatile manganese compounds Within the furnace through the inter-reaction of the gases, as the volatile mangano-nitrogen compounds are very susceptible to oxidizing influences, manganese having such an affinity for oxygen that' it is -capable 'of decomposlngwater even at ordi` nary temperatures. Any oxidizing of these volatile compounds deposits carbon and manganese compounds and releases inert nitrogen. ln practice therefore the heat by which the' required temperatures are attained is partially provided by the electric resistance and partially by combustiom an,

excess of carbon being continually supplied to the furnace. As the products passing below the electrodes are mostly carbon, the twyers are .adapted to supply oxygen to consume this excess of carbon. The residue material passing downward to the grinding linings 10 and l1, is there broken up fine enough to be removed from the furnace when the shell rotates, these products consisting of carbon and impurities which cannot readily be slagged and must therefore be removed from the furnace by crushing. lt Will be apparent that either the shell or furnace shown permits the products of combustion land likewise subjects all parts of the charge to a uniform temperature as all portions of the charge are forced .to pass between the electrodes and are thereby uniformly heated. The cliare is also uniformly subjected to the action of the twyers for the removal of part of the excess carbon and the residue is lina-lly ground fine enough for removal. It will be evident that this automatic regu ation and uniform treatment may likewise be utilized for other purposes than the preparation of nitrogenous compounds or for the preparation of compounds of nitrogen by other than manganese compounds, such as nitrids,car-

bids, cyanids, etc.'

ln actual operation the `furnace may be revolved slowly and continuously or it may be operated only at intervals as the removal of refuse and the feeding of -material requires. ln practice this is determined by the conditions of operation and Whether the volatile products are affected by the incoming oxidized' products. By reducing and controlling the amount of carbon fed to the furnace and removing the products before the volatile combinations With the nitrogen are formed or distilled or by controlling and limiting the access of nitrogen and carbon monoxid which are largely instrumental in producing the volatile compounds as nitro-carbonyl compounds, the furnace may be used for carbid or nitrid manufacture. lllhen carbid of manganese is one of the products it may be used for the production of methane for gas enrichment. The outlet gases from the pipe 23 contain combustible gases and these maybe used as producer gas.

. l claim:

l. The process of forming nitrogenous compounds and the like, comprising heating manganese-containing material With carbonaceous material'in the presence'of nitrogenous material..

2. The process of producing nitrogenous materials and the like, which consists `in heating manganiferous material in the presence -of carbona'ceous material and a gas containing nitrogen.

The process of producing nitrogenous material which consists in. heating e `ture of mangeniereus esrboneeeons atile compounds, which eensists in heatingr zr mixture Vo" manganierous and esrhoneeeous rnateriai and forcingnitrogen-centaining gas therethrough.

5.l The process of forming veietiie trogenous compounds eonsistingin hestinge mixture of msngenierons and eerhoneceous material, passingr nitrogen-Containing gases therethrough, drawing oi? the Vole'tie presin uct and condensing the letter.

6. The dprocess of producing nitrogenous Compounds which consists in forming-a mixture of msngeniferous and eerbonaeeeus materials, passing 'e heating electric current therethrough and injecting nitrogen containing gases thereints.

7. The process et produeing nitrogenons eonipounds, which consists in forming s mixture of manganese exis?.` metV carboneeeous nieteriei and passing nitrogemconteliningl gases 'merethrough,s

8., The process of producing nitrogenous eompo'rinds'which consists in forming' a miX- tureo manganese @Kid and 'eerbonaceous material, passing :t hes'tingeieetre current therethrough and injecting nitrogen-Congases thereinto, The process of forming voistile nitrogenous laen/1ponns, which consists in mixingmsngsni'ferous and earbonaceous meterisls, passing 'them continuously between veieetrocies suppying heating current and injeeting'e mixture of oxygen and nitrogen inte said mixture beneath said. electrooles.

JOHN B5. MAGAUmY, .ennn'r DOBBERMAN. 

